Toilet detergent composition containing synergistic di- and tri-halo salicylanilide mixtures



p 1959 H. c. STECKER' 2,906,711

- TOILET DETERGENT COMPOSITION CONTAINING SYNERGISTIC DI- AND TRI-HALO SALICYLANILIDE MIXTURES Filed April 25, 1958 SKIN swsTANTMTY TET5 2 B I I Z I I I I 5 t g I v A r \L I u l g N v I PERCFNT 1544a; N 5,

m 60 7o 80 90 mo United States Patent F TOILET DETERGENT COMPOSITION CONTAIN- ING SYNERGISTIC DI-AND TRI-HALO SALICYL- ANILIDE MIXTURES Herbert C. Stacker, Hohokus, NJ. Application April 25, 1958,5SerialNo. 730,910 1 Claim. (Cl. 252-406) in use or do not have a substantive or lasting elfect,

on the skin.

The compounds employed with toilet detergent compositions of the present invention may be designated broadly by the following general chemical structural formulas, wherein the letter X denotes a halogen atom:

5,4'-dihalosalicylanilides O H II I X C- 3,5 ,4-trihalosalicylanilides It has been found that certain mixtures of the diand tri-halo salicylanilides disclosed above process synergistic substantive properties with respect to the skin whereby an unusual lasting germicidal effect is obtained when they are used in toilet detergent compositions. This effect can he more readily understood by reference to the examples and to the accompanying drawing which is based on some of these examples.

Example 1 Serial wash basin tests were conducted using the Cade method as described in Soap and Sanitary Chemicals, 26, 35 (1950), as follows:

The material to be used as a germicide wlas milled dry in a concentration of 0.5% into Ivory brand soap, which is a neutral white high grade toilet soap consisting of a mixture of 80% sodium soap and 20% potassium soap produced from a 70% tallow and 30% coconut oil glyceride blend (made in accordance with U.S. Patent 2,295,594). A thick paste was prepared by the addition of water, and the soap was pressed into molds. Human subjects then washed their hands with this soap and the reduction of germicidal power (in the V 2,906,711 Patented Sept. 29, 1959 2 hand count) at the end of the testwas determined with the following results obtained: f

1 Number Percent Germlclde of subreduction jects in hand count 5,4-dibromo SA 10 N one 3,5,4-tribromo SA 10 It will be noted from the foregoing results that the 5 ,4'-dibromosalicylanide possessed no substantivity on the skin and showedno reduction in hand count, whereas the 3,5,4'-tribromosalicylanilide showed a 65% reduction at the end of the test.

At times, the word salicylanilide shall be referred to in this application as SA.

Example 2 Germlelde Zone of Percent Inhibi- Percent Percent r tion, mm.

3,5,4- 5, triBrSA diBrSA The results of these tests are plotted in the graph depicted in the single figure of the accompanying drawing. Curve A is a straight line between the zero and 100% points on which the experimental test points would have fallen if the germicidal etfectiveness of the two compounds were arithmetically additive. Actually, however, the test points fall on curve B, showing that, in the higher percentages of 3,5 ,4'-triBrSA in 5,4'-diBrSA, there was a marked synergistic effect of the otherwise entirely inelfective dibromo derivative in the tribromo compound. At the peak value between 75% and 90% of the tribromo derivative, the effectiveness of the mixture is of the effectiveness of the pure tribromo compound. It also is noted that the shaded area C which includes mixtures containing 65% to 98% of the tribromo derivative are unexpectedly and unusually high in germicidal effect, having an etfectiveness of at least 144% of that of the pure tribromo derivative. It is this range which is being claimed in the present application.

Commercial toilet soaps generally consist of neutral high grade sodium and potassium salts of tallow fatty acids. The concentration of the present synergistic mixture used in such soaps may be 0.01% to 0.5% or to 1%, 2%, 5%, or even 10% by weight of the soap.

It has been found that similar results are obtained with other diand trihalosalicylanilide mixtures containing 3,5,4'-triiodo SA, 3,5,4-trichloro SA, 3,5-dibromo-4.

3 chloro SA, with 5,4'-dichloro SA, 5 ch1oro-4'-bromo SA, 5-bromo-4-chloro SA, and'the like. The most desirable compounds are the bromo and/ or chloro compounds.

The aforesaid halosalicylanilides may be prepared by the method disclosed in US. Patent 2,731,386. For example, 5,4-dichloro SA can be prepared by heating 5- chlorosalol with 4-chloro-aniline to 180-220 C. and continuously distilling off the liberated phenol during the process. It is advantageous to use reduced pressure for this distillation and to carry out the procedure in a nitrogen atmosphere. The crude reaction product is dissolved in alcohol to which an equivalent amount of sodium hydroxide is added in the form of approximately N aqueous solution. The resulting solution of the sodium salt of 5,4'-dichloro SA then is discolorized with charcoal and neutralized with dilute hydrochloric acid. The 5,4-dichloro SA thus precipitated is filtered and recrystallized from ethyl alcohol, ethyl acetate, or some other suitable solvent.

A further method involves condensation between the salicylic and aniline moieties in an organic solvent such as toluene, chlorobenzene, kerosene, etc., in presence of a dehydrating agent such as thionyl chloride. The benzene nuclei may be halogenated prior to or after condensation by application of the proper halogen in a glacial acetic acid or acetic acid-water mixture containing the halogenatable materials.

Commercial synthetic toilet detergent compositions generally consist of neutral high grade sodium and potassium salts of tallow fatty acids, some of which may contain a small amount (110%), medium amount (10- 50%), or even a major amount (SO-100%) of non-soap synthetic organic detergents, particularly the anionic detergents such as the substituted amides and the alkyl aryl sulfonates. The term detergent includes soap,

4 as well as such synthetic detergents and other detergents such as fatty alcohol sulfates, fatty acid amides, sodium tripolyphosphates, and combinations thereof. The term toilet detergen as used herein is employed to designate a composition employed for washing the skin. The term toilet soap used herein also is employed in its popular or ordinary meaning, that is, those compositions employed for cleansing the skin and prepared from an alkali metal compound such as potassium or sodium hydroxide and a fat or fatty acid, both saturated and unsaturated. The compositions described herein also may include other antiseptic agents, emollients, water softeners, antioxidants, dyes, perfumes, cold cream additives and the like.

This application is a continuation-in-part of copending application Serial No. 653,737, filed by Herbert C. Stecker on April 19, 1957 (now abandoned).

I claim:

An antiseptic toilet detergent composition comprising a synthetic organic toilet detergent and 0.01% to 10% by weight based on the detergent of a germicide consisting of a synergistic mixture of to 98% by weight of 3,5,4'-trihalosalicylanilide and 35% to 2% of 5,4- dihalosalicylanilide, wherein the halo substituents are selected from the group consisting of chlorine, bromine and iodine.

References Cited in the file of this patent UNITED STATES PATENTS 2,731,386 Reiner Jan. 17, 1956 2,802,029 Schuler Aug. 6, 1957 FOREIGN PATENTS 1,066,216 France Jan. 20, 1954 760,210 Great Britain Oct. 31, 1956 

